Photocatalytic Assembly of Structurally Diverse α ‐Trifluoromethyl Tertiary Amines Using Benign Nitrogen Donors

α‐Trifluoromethyl amines are privileged motifs in drug design. Traditional assembly of α‐trifluoromethyl amines relies on harsh conditions and toxic reagents, prompting the demand for milder, atom‐economical methods. While alkene carboamination offers a modular access to diverse amines, the aminative difunctionalization of trifluoromethyl alkenes pose challenges due to facile defluorination. Herein, we report two visible light‐induced protocols for the aminative difunctionalization of α‐trifluoromethyl styrenes using benign nitrogen sources—nitriles and oximes—instead of prior toxic azides. A photoredox approach leads to the arylamination of α‐trifluoromethyl alkenes and radical oxidation, leveraging nitriles to capture benzyl carbocations, while a complementary alkylamination strategy exploits the decarboxylative decomposion of alkyl oxime esters and installs C ‐ and N ‐radicals on the double bond with regiospecificity. These two protocols constitute flexible access to diverse α‐trifluoromethyl tertiary amines under sustainable conditions. Only N 2 or CO 2 are emitted as byproducts. Scalability, broad substrate tolerance, and high yields highlight the practicality of this methodology.